Materials Chemistry

905 Pages·2023·22.008 MB·English

by  Bradley D. Fahlman

Bradley D. Fahlman
Materials
Chemistry
Fourth Edition
Materials Chemistry
Bradley D. Fahlman
Materials Chemistry
Fourth Edition
Bradley D. Fahlman
Department of Chemistry and Biochemistry
Central Michigan University
Mount Pleasant, MI, USA
ISBN 978-3-031-18783-4 ISBN 978-3-031-18784-1 (eBook)
https://doi.org/10.1007/978-3-031-18784-1
1st &2nd editions: © Springer Science+Business Media B.V. 2007, 2011
3rd edition: © Springer Nature B.V. 2018
4th edition: © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer
Nature Switzerland AG 2023
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Preface
As we surge ahead with global electrification of the transportation industry, advanced
materials will continue to play a critical role—not only for the battery packs—but
also to expand the electrical grid needed to enable the impending surge in power use.
However, beyond the transportation sector, breakthroughs in materials design will
also be essential to help us address the effects of climate change and energy shortages,
homeland security threats, and to fight next-generation diseases. An increasing focus
on sustainability within the framework of a circular economy will also be needed
to ensure that nonrenewable resources remain available for future generations. It is
truly exciting to think about the potential breakthroughs coming in the next few years
as artificial intelligence (AI) and machine learning (ML) have greatly expanded our
capacity in the design of novel materials. The next steps in our technological journey
are governed only by our creativity and steadfast ability to apply fundamental scien-
tific knowledge. This latter quality represents the overarching goal of this textbook—
to provide a suitable breadth and depth coverage of various classes of materials to
help enable the development of next-generation devices and applications.
As with previous editions, Materials Chemistry focuses on the ‘structure vs. prop-
erty’ assessment of both inorganic and organic materials, from their bulk to nanos-
tructure regime. The content presented herein is most appropriate for junior or senior
undergraduate students, as well as first-year graduate students in chemistry, physics,
and engineering disciplines. In addition, this textbook has also been widely used by
researchers in industry as a primer to learn about various materials classes or charac-
terization techniques. Each chapter includes a comprehensive reference list, which
is essential for more detailed research.
For such a broad and rapidly evolving field as materials chemistry, it is a daunting
task to remain contemporary. However, we have attempted to do so through extensive
updates and expansions to provide an innovative and practical perspective throughout.
After providing a historical perspective in the first chapter, this edition provides an
expanded discussion of sustainability—a topic that is often overlooked in our zeal to
fabricate faster and better devices—but absolutely essential to ensure the survival of
future generations. In addition to reorganization and rewriting for clarity throughout,
this edition includes the following new sections:
v
vi Preface
●
Materials design via combinatorial and machine learning approaches (Chap. 1)
●
Kroger-Vink notation for defects (Chap. 2)
●
Additive manufacturing (AM) for metallurgy (Chap. 3)
●
Negative capacitance field effect transistors (NCFETs; Chap. 4)
●
3-D printing of polymers (Chap. 5)
●
New toxicity studies of nanomaterials (Chap. 6)
●
Core-shell quantum dots (Chap. 6)
●
Heat-assisted magnetic recording (Chap. 6)
●
Dynamic light scattering (DLS) techniques (Chap. 7).
In addition, the section related to nanotoxicity was extensively updated to reflect
the latest discoveries. This book also continues to be the first to provide detailed
processing information for the latest technology node of integrated circuit design,
based on FinFETs. Over 100 additional references were added throughout this
edition, and the end-of-chapter questions and bibliographies were extensively revised
to reflect the current state of the art.
As with previous editions, Appendices are also provided that contain an updated
and expanded timeline of major materials development and the complete transcript
of Nobel Laureate Feynman’s speech “There’s Plenty of Room at the Bottom”. A
collection of materials-related laboratory experiments is also included, which are
suitable for both undergraduate or graduate curricula.
I wish to thank my wife, Diyonn, for her love and continued support and encour-
agement. Our frequent travels across an expansive globe continually remind me how
fortunate I am to have found my true soulmate. Our two kitties, Cash and Sissy, also
played a role in the 4th edition by reminding me when to take cuddle breaks!
I also am extremely appreciative for the input provided by students and instructors
who have either adopted, or have considered the adoption, of Materials Chemistry.I
continue to offer thanks to every reader of this book and solicit your comments to my
email ([email protected]). Please let me know what you think of this edition; I
promise to incorporate your suggestions to strengthen future editions.
Mount Pleasant, MI, USA Bradley D. Fahlman, Ph.D.
January 2023
Contents
1 What is “Materials Chemistry”? ................................. 1
1.1 Historical Perspectives ...................................... 2
1.2 “Bottom-Up” Materials Synthesis ............................. 5
1.3 Materials Discovery ........................................ 6
1.4 Materials Sustainability ..................................... 12
Further Reading ................................................. 29
2 Solid-State Chemistry .......................................... 31
2.1 Structural Order ............................................ 31
2.2 Bonding in Solids I: Intermolecular Forces ..................... 32
2.2.1 Ionic Solids ......................................... 33
2.2.2 Metallic Solids ...................................... 35
2.2.3 Covalent Network Solids .............................. 36
2.2.4 Molecular Solids ..................................... 36
2.3 Bonding in Solids II: Band Theory ............................ 40
2.4 The Crystalline State ........................................ 45
2.4.1 Crystal Growth Techniques ............................ 49
2.4.2 Crystal Structures .................................... 52
2.4.3 Crystal Symmetry and Space Groups ................... 59
2.4.4 Archetypical Interstitial Crystal Lattices ................. 71
2.4.5 Superconductivity of Perovskites: Toward
a Room-Temperature Superconductor ................... 87
2.4.6 Crystal Imperfections ................................. 94
2.4.7 Physical Properties of Crystals ......................... 112
2.5 Ceramics .................................................. 128
2.5.1 Sol–Gel Processing ................................... 134
2.5.2 Cementitious Materials ............................... 139
2.5.3 Biomaterials Applications ............................. 144
2.6 Glasses ................................................... 147
2.7 Solid-State Case Study I: Solid Electrolytes for Energy
Storage Applications ........................................ 159
vii
viii Contents
2.8 Solid-State Case Study II: Porous Materials: Zeolites
And Metal–Organic Frameworks (MOFs) ...................... 166
Further Reading ................................................. 188
3 Metals ......................................................... 191
3.1 Mining and Processing of Metals ............................. 191
3.1.1 Powder Metallurgy ................................... 206
3.1.2 Additive Manufacturing (AM) ......................... 212
3.2 Metallic Structures and Properties ............................ 213
3.2.1 Phase Behavior of Iron-Carbon Alloys .................. 215
3.2.2 Hardening Mechanisms of Steels ....................... 222
3.2.3 Stainless Steels ...................................... 237
3.2.4 Nonferrous Metals and Alloys ......................... 242
3.3 Metal Surface Treatments for Corrosion Resistance .............. 263
3.4 Magnetism ................................................ 266
3.5 Metals Case Study: Hydrogen Storage ......................... 276
Further Reading ................................................. 288
4 Semiconductors ................................................ 291
4.1 Properties and Types of Semiconductors ....................... 291
4.2 Silicon-Based Applications .................................. 299
4.2.1 Silicon Wafer Production .............................. 300
4.2.2 Integrated Circuits ................................... 303
4.2.3 Field-Effect Transistors (FETs) ........................ 305
4.2.4 Transistor Scaling: Advantages and Limitations .......... 312
4.2.5 Integrated Circuit Fabrication .......................... 324
4.2.6 Thin-Film Deposition Methodologies ................... 350
4.3 Light-Emitting Diodes: There is Life Outside of Silicon! ......... 367
4.4 Thermoelectric (TE) Materials ............................... 377
4.5 Semiconductors Case Study: Photovoltaic (Solar) Cells .......... 383
Further Reading ................................................. 404
5 Polymeric Materials ............................................ 407
5.1 Polymer Classifications and Nomenclature ..................... 408
5.2 Polymerization Mechanisms ................................. 416
5.3 “Soft Materials” Applications: Structure Versus Properties ........ 448
5.3.1 3-D Printing ......................................... 452
5.3.2 Biomaterials Applications ............................. 464
5.3.3 Conductive Polymers ................................. 485
5.3.4 “Soft” Lithography ................................... 495
5.4 Polymer Additives .......................................... 503
Further Readings ................................................ 531
Contents ix
6 Nanomaterials ................................................. 533
6.1 The Toxicity of Nanomaterials ............................... 534
6.2 What is “Nanotechnology”? .................................. 556
6.3 Nanoscale Building Blocks and Applications ................... 558
6.3.1 Zero-Dimensional Nanomaterials ...................... 562
6.3.2 One-Dimensional Nanostructures ...................... 625
6.3.3 Two-Dimensional Nanostructures ...................... 660
6.4 Important Nanomaterials Applications I: Lithium-Ion
Batteries .................................................. 670
6.5 Important Nanomaterials Applications II:
Nanoelectromechanical Systems (NEMS) ...................... 678
Further Reading ................................................. 718
7 Materials Characterization ...................................... 721
7.1 Light Scattering ............................................ 722
7.2 X-ray Scattering ............................................ 727
7.2.1 X-ray Diffraction (XRD) .............................. 731
7.2.2 Small-Angle X-ray Scattering (SAXS) .................. 743
7.3 Optical Microscopy ......................................... 744
7.4 Electron Microscopy ........................................ 747
7.4.1 Transmission Electron Microscopy (TEM) ............... 756
7.4.2 Scanning Electron Microscopy (SEM) .................. 776
7.5 Surface Characterization Techniques Based on Particle
Bombardment .............................................. 788
7.5.1 Photoelectron Spectroscopy (PES) ...................... 788
7.5.2 X-ray Absorption Fine Structure (XAFS) ................ 790
7.5.3 Ion-Bombardment Techniques ......................... 792
7.5.4 Atom-Probe Tomography (APT) ....................... 803
7.6 Scanning Probe Microscopy (SPM) ........................... 804
7.7 Bulk Characterization Techniques ............................. 811
Further Reading ................................................. 829
Appendix A: Timeline of Materials and Technological Discoveries ...... 831
Appendix B: “There’s Plenty of Room at the Bottom” ................ 845
Appendix C: Materials-Related Laboratory Experiments ............. 857
Index ............................................................. 885
Chapter 1
What is “Materials Chemistry”?
Life in the twenty-first century is ever-dependent on an unlimited variety of advanced
materials. In our consumptive world, it is easy to take for granted the macro-, micro-,
and nanoscale building blocks that comprise any item ever produced. We are spoiled
by the technology that adds convenience to our lives such as microwave ovens, laptop
computers, cell phones and tablets, and improved modes of transportation. However,
we rarely take time to think about and appreciate the materials that constitute these
modern engineering feats.
The term material may be broadly defined as any solid-state substance or device
that may be used to address a current or future societal need.1 For instance, simple
building materials such as glass, wood, aluminum, etc. address our need of shelter.
Other more intangible materials such as nanoscale components are also considered
as materials, even if a particular nanomaterial may not yet be widely proven for
applications.2
A general classification of various types of materials is illustrated in Fig. 1.1.
Although this indicates sharp distinctions between various classes, there is often
ambiguity regarding the proper taxonomy for a specific material. For example, a thin
film is defined as having a thickness of less than 1 µm; however, if the thickness drops
to below 100 nm, the film may be more accurately classified as a 2-D nanomaterial.3
Likewise, liquid crystals are best described as having properties intermediate between
amorphous and crystalline phases, and composites typically involve both inorganic
and organic components.
The broadly defined discipline of materials chemistry is focused on understanding
the relationships between the arrangement of atoms, ions, or molecules comprising
a material, and its physical and chemical properties. By this designation, common
disciplines such as polymer, solid-state, and surface chemistry would all be placed
within the scope of materials chemistry. This broad field consists of studying the
structure and properties of existing materials, synthesizing and characterizing new
materials, and using advanced computational techniques to understand the properties
of existing materials or those that have not yet been fabricated.
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 1
B. D. Fahlman, Materials Chemistry,
https://doi.org/10.1007/978-3-031-18784-1_1